全硅MCM-41担载的Ni-W催化剂上二苯并噻吩加氢脱硫反应动力学研究  

STUDY ON HYDRODESULFURIZATION KINETICS OF DIBENZOTHIOPHENE OVER Ni-W SULFIDES SUPPORTED BY SILICEOUS MCM-41

作　　者：李翔[1] 王安杰[1] 孙仲超[1] 李矗[1] 胡永康[2] 

机构地区：[1]大连理工大学精细化工国家重点实验室,辽宁大连116012 [2]抚顺石油化工研究院,辽宁抚顺113001

出　　处：《石油学报（石油加工）》2003年第4期1-7,共7页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家自然科学基金青年基金资助项目 ( 2 0 0 0 30 0 2 );辽宁省中青年学科带头人资助项目

摘　　要：以二苯并噻吩 (DBT)的质量分数为 0 .2 %～ 0 .8%的十氢萘溶液为模型化合物 ,在中压固定床反应器上 ,研究了全硅MCM 41担载的Ni W硫化物催化剂上的加氢脱硫反应 (HDS)动力学。理论分析和实验结果都表明 ,常用的Langmiur Hinshelwood方程不适用于气 液 固三相滴流床积分反应器。应用假 1级平推流反应模型 ,分别得到了各催化剂作用下的该反应的速率常数和表观活化能。催化剂的Ni/W摩尔比 (nNi/nW)为 0 .2 5、 0 .5、0 .75和 1.0时 ,该催化HDS反应的表观活化能分别为 117.3、 96.7、 64 .4和 72 .9kJ/mol。其中 ,nNi/nW =0 .75的反应表观活化能最低。将催化剂的HDS活性与表观活化能相关联可以发现 ,表观活化能和催化剂活性之间有对应关系 ,表观活化能越低 。The kinetics of hydrodesulfrization (HDS) of dibenzothiophene (DBT) catalyzed by Ni W/Si MCM 41 catalyst was studied.Both the theoretical analysis and the experimental results indicated that the Langmiur Hinshelwood model was not suitable for the kinetics of trickle bed integrated reactor,involving transportation among gas liquid solid three phases.The rate constants of HDS were well correlated to a pseudo first order plug flow reaction model.The apparent activation energy of HDS was calculated by the Arrhenius equation and changed with the Ni/W atomic ratio in catalyst.The apparent activation energy were 117.3,96.7,64.4 and 72.9?kJ/mol corresponding to the Ni/W atomic ratio of 0.25,0.50,0.75 and 1.0,respectively.HDS reaction showed the lowest apparent activation energy on the catalyst with the Ni/W atomic ratio of 0.75 .The correlation between apparent activation energy and HDS reactivity revealed that the catalyst with low apparent activation energy exhibited high performance in HDS of DBT.

关 键 词：全硅MCM-41 Ni—W催化剂 二苯并噻吩 加氢脱硫 反应动力学 石油炼制 

分 类 号：TE624.431[石油与天然气工程—油气加工工程] TE624.9